Silica nanoparticles, synthesis using

Dye-Doped Silica Nanoparticle Synthesis Using Nonionic Surfactant-Based... 

Qian, L., and X. R. Yang, 2007. One-step synthesis of Ru(2,2 -bipyridine)(3)Cl-2-immobilized silica nanoparticles for use in electrogenerated chemiluminescence detection. Adv Func Mater 17 1353-58. 

The acidic conditions of standard SBA-15 synthesis [35] cause the precipitation of metal nanoparticles without silica encapsulation, or the formation of amorphous silica due to the presence of the polymer used for nanoparticle synthesis. Therefore, the SBA-15 framework was synthesized under neutral condition using sodium fluoride as a hydrolysis catalyst and tetramethylorthosilicate (TMOS) as the silica precursor. Pt particles with different sizes were dispersed in the aqueous template polymer solution sodium fluoride and TMOS were added to the reaction mixture. The slurry aged at 313 K for a day, followed by an additional day at 373 K. Pt(X)/SBA-15-NE (X = 1.7, 2.9, 3.6, and 7.1nm) catalysts were obtained by ex-situ calcination (see Section 3.2). TEM images of the ordered... 

By using other templates, the size of metal nanoparticles can be also controlled. Chen et al. reported the sonochemical reduction of Au(III), Ag(I) and Pd(II) and synthesis of Au, Ag and Pd nanoparticles loaded within mesoporous silica [48,49]. Zhu et al. also reported the sonochemical reduction of Mn04 to Mn02 and synthesis of Mn02 nanoparticles inside the pore channels of ordered mesoporous cabon [50]. Taking into account these reports, the rigid pore of inorganic materials can be used as a template for the size controlled metal nanoparticle synthesis even in the presence of ultrasound. 

Figure 5.9 Synthesis of gold nanoparticles within Zr02. A gold colloid is first prepared then coated with silica using a modified Stober process [75]. The silica is removed using NaOH. Reproduced with permission from [74],...

Generally, two common methods, the Stober method and the reverse microemulsion method are used for synthesis of silica nanoparticles. As derivatives of a sol-gel process, both methods involve hydrolysis of a silicon alkoxide precursor to form a hydroxysilicate followed by polycondensation of the hydroxysilicate to form a silica nanoparticle [44]. 

The Stober method is also known as a sol-gel method [44, 45], It was named after Stober who first reported the sol-gel synthesis of colloid silica particles in 1968 [45]. In a typical Stober method, silicon alkoxide precursors such as tetramethylorthosili-cate (TMOS) and tetraethylorthosihcate (TEOS), are hydrolyzed in a mixture of water and ethanol. This hydrolysis can be catalyzed by either an acid or a base. In sol-gel processes, an acidic catalyst is preferred to prepare gel structure and a basic catalyst is widely used to synthesize discrete silica nanoparticles. Usually ammonium hydroxide is used as the catalyst in a Stober synthesis. With vigorous stirring, condensation of hydrolyzed monomers is carried out for a certain reaction time period. The resultant silica particles have a nanometer to micrometer size range. 

In summary, a suitable association between dye molecules and the silica matrix is necessary for synthesis of DDSNs. Without the presence of chemical bonds or electronic interactions, the dye molecules will leak out from silica nanoparticles through the silica pores [22], Such DDSNs will provide unstable florescence signals and cannot be used as a labeling agent in bioanalysis. Meanwhile, water solubility is critical for a dye molecule when using a reverse microemulsion method to make the DDSNs. 

Traditionally, the sol-gel process has been used for the preparation of silica nanoparticles via the hydrolysis of alkoxides in organic solvents [52,53]. Similar hydrolysis and condensation carried out in w/o microemulsion offers robust control over the synthesis process. W/o emiflsion-mediated sol-gel synthesis is currently used for the fabrication of pure sihca, as well as inorganic and organic dye-doped silica nanoparticles. The synthesis of sihca and dye-doped nanoparticles is classified in the following sections on the basis of the classification of the head group fimctionahty of the major surfactant used. 

From our research group Santra et al. [11,41,42] reported the development of novel luminescent nanoparticles composed of inorganic luminescent dye RuBpy, doped inside a sihca network. These dye-doped silica nanoparticles were synthesized using a w/o microemulsion of Tx-lOO/cyclohexane/ n-hexanol/water in which controlled hydrolysis of the TEOS leads to the formation of mono dispersed nanoparticles ranging from 5-400 nm. This research illustrates the efficiency of the microemulsion technique for the synthesis of uniform nanoparticles. These nanoparticles are suitable for biomarker application since they are much smaller than the cellular dimension and they are highly photostable in comparison to most commonly used organic dyes. It was shown that maximum liuninescence intensity was achieved when the dye content was around 20%. Moreover, for demonstration... 

Suzuki K, Ikari K, Imai H (2004) Synthesis of silica nanoparticles having a well-ordered mesostructure using a double surfactant system. J Am Chem Soc 126 462-463... 

Silica Nanoparticles. The base-catalyzed hydrolysis of silicon aikoxides in microemulsions produces nanoparticles (20-39). Aqueous ammonia has been used primarily as the base, with AOT and nonionic polyoxyethylene ethers as the main surfactants. Figure 2.2.6 presents a flow diagram for the synthesis of pure silica (23-32) the microemulsion is first prepared and then the alkoxide is added. As can be seen from Table 2.2.1, the microemulsions include the systems AOT/ isooctane/water/ammonia, AOT/toluene/water/ammonia, NP-5/cyclohexane/water/ ammonia, and NP-4/heptane/water/ammonia. Typical reaction times are l -5 days. Various modified silica nanoparticles have also been prepared, including hydropho-... 

NIL patterns were also used for the assembly of nanoparticles via supramole-cular host-guest interactions.95 The NIL-patterned substrate was functionalized with CD SAMs via a three-step synthesis process. The fabrication of 3D nanostructures was achieved by the alternating assembly of multivalent guest-functionalized dendrimers and CD-fnnctionalized Au nanoparticles.88 This methodology can be applied to various nanoparticles, regardless of their size and core material. For instance, CD-functionalized silica and polystyrene nanoparticles were adsorbed onto NIL-patterned CD SAMs with preadsorbed guest-fnnctionalized dendrimers.60 92 Recently, Huskens et al. demonstrated the supramolecular LbL assembly of 3D multicomponent nanostructures of nanoparticles by alternating assembly steps of complementary ferrocenyl-functionalized silica nanoparticles and different kinds of host-fnnctionalized nanoparticles (see Fig. 13.8).66... 

Segmented gas-liquid (Taylor) flow was used for particle synthesis within the liquid slugs. Tetraethylorthosilicate in ethanol was hydrolyzed by a solution of ammonia, water and ethanol (Stober synthesis) [329]. The resulting silicic acid monomer Si (OH)4 is then converted by polycondensation to colloidal monodisperse silica nanoparticles. These particles have industrial application, for example, in pigments, catalysts, sensors, health care, antireflective coatings and chromatography. 

One of the first examples of mesoscopic-macroscopic two-dimensional ordering within a structure involved a bacterial superstructure formed from the co-aligned multicellular filaments of Bacillus subtilis that was used to template macroporous fibers of either amorphous or ordered mesoporous silica [82], The interfilament space was mineralized with mesoporous silica and, following removal of the organic, a macroporous framework with 0.5 pm wide channels remained. Mesoporous silica channel walls in this hierarchical structure were curved and approximately 100 nm in thickness. Dense, amorphous walls were obtained by replacing the surfactant-silicate synthesis mixture with a silica sol solution. The difference in the mode of formation between porous and non-porous wall structures was explained in terms of assembly from close-packed mesoporous silica coated bacterial filaments in the former compared to consolidation of silica nanoparticles within interfilament voids in the latter. 

K. Suzuki, K. Ikari, and H. Imai, Synthesis of Silica Nanoparticles having a Well-ordered Mesostructure using a Double Surfactant System. J. Am. Chem. Soc., 2004, 126, 462 163. 

Fu, X.A. and Qutubuddin. S., Synthesis of titania-coated silica nanoparticles using ono-ionic water-in-oil. Colloids Sutf. A. 178. 151. 2001. 

Different inorganic materials have been used as supports in SAPC glass beads of controlled pore size [6,14—17, 24, 39—42,44,45, 53] porous [11,15,18,19, 21, 23, 28-32, 35, 36, 38, 39, 43, 48, 49] and nonporous [28, 33, 48] silica nanoparticles synthetic phosphate [27] carbon [39], and alumina [15,39]. It was shown that glass beads, siKca, and synthetic phosphate gave the best performance. All these supports have a high specific surface with an average diameter of the pores, in the case of porous supports, between 60 and 345 A. The use of chitosan as a natural polymeric support of SAP catalysts for the synthesis of fine chemicals has been reported recently [54]. 

Making use of constrained polymerisation of divinylbenzene on surfactant-modified colloid silica, Jang and Lim prepared carbon nanocapsules and mesocellular foams. Later, they reported that mesoporous carbons with highly uniform and tunable mesopores were fabricated by one-step vapour deposition polymerisation using colloidal silica nanoparticles as template and polyacrylonitrile as carbon precursor. Hampsey et al. recently reported the synthesis of spherical mesoporous carbons via an aerosol-based, one-step approach using colloidal silica particles and/or silicate clusters as template. ... 

Muller and coworkers prepared disc-like polymer Janus particles from assembled films of the triblock copolymer SBM and, after hydrolysis of the ester groups into methacrylic acid units, used these as Pickering stabilizer in the soap-free emulsion polymerization of styrene and butyl acrylate [111]. Armes and coworkers described the synthesis of PMMA/siUca nanocomposite particles in aqueous alcoholic media using silica nanoparticles as stabilizer [112], extending this method to operate in water with a glycerol-modified silica sol [113, 114]. Sacanna showed that methacryloxypropyltrimethoxysilane [115] in the presence of nanosized silica led to spontaneous emulsification in water, which upon a two-step polymerization procedure afforded armored particles with an outer shell of PMMA [116]. Bon and coworkers demonstrated the preparation of armored hybrid polymer latex particles via emulsion polymerization of methyl methacrylate and ethyl methacrylate stabilized by unmodified silica nanoparticles (Ludox TM O) [117]. Performance of an additional conventional seeded emulsion polymerization step provided a straightforward route to more complex multilayered nanocomposite polymer colloids (see Fig. 14). 

Ma and Dai [121] reported the synthesis of polystyrene latexes armored with silica nanoparticles (10-15nm in diameter, PA-ST silica sol, Nissan Chemicals) via solids-stabilized emulsion polymerization. They used VA-086, 2,2 -azobis [2-methyl-lV-(2-hydroxyethyl)propionamide], as nonionic initiator. Whereas we found that Pickering emulsion polymerization of styrene using Ludox TM-40 and a low flux of radicals generated from potassium persulfate did not result in an armored latex, the hydroxyethyl groups probably enhance the wettability of the surface of the latex particles to promote silica adhesion. This was confirmed by a... 

FIGURE 6.8 (a) Schematic illustration of the procedure for the synthesis of polymeric capsules based on surface-initiated RAFT polymerization using silica nanoparticles as templates, (b) TEM image of polymer grafted silica nanoparticles, (c) SEM and (d) TEM images of the synthesized polymeric capsules. Source Huang et al. [15]. Reproduced with permission of American Chemical Society. 

Modification of mesoporous silica nanoparticles using the bifunctional strategy, post-synthesis grafting, and backfilling strategy in order to make them suitable for drug delivery applications was reported (Lu et al. 2007). The modified nanoparticles were able to deliver the water insoluble drug camptothecin into different types of human cancer cells (Johansson et al. 2008). 

---